Thiol and dithiol carbamate acid ester derivatives of phenyl formamidine

ABSTRACT

wherein R1 represents hydrogen, alkyl, alkenyl, alkinyl, or aralkyl, R2 represents alkyl, alkenyl, alkinyl, alkoxyalkyl, alkylthioalkyl, or aralkyl, (R3)n represents one or more similar or different radicals, such as hydrogen, halogen, alkyl, alkoxy, alkylthio, alkenyloxy, cyano, nitro, dialkylamino, or carbalkoxy, n is 1 to 5, and X represents oxygen or sulphur, processes for their manufacture and their use in pest control. Thio- and dithiocarbamate formamidines of the formula

United States Patent [191 Pissiotas 1 July 29,1975

i 1 THiOL AND DlTiilOL CARBAMATE ACID ESTER DERIVATIVES OF PHENYL FORMAMIDINE [75] inventor: Georg Pissiotas, Lorrach, Germany [73] Assignee: Ciba-Geigy Corporation, Ardsiey,

[22] Filed: Oct 9, I973 [21] Appl. No.: 404,467

[30] Foreign Application Priority Data Primary Examiner-Lewis Gotta Assislant Examiner-D. R. Phillips Attorney, Agent, or Firm-Harry Falber; Frederick H. Rubin 1571 ABSTRACT Thioand dithiocarbamute formamidines of the formula (R:)- 7 RI wherein R represents hydrogen, alkyi, alkenyl, alki- 'nyl, or aralkyl, R, represents alkyi, alkenyl, aikinyl,

alkoxyalkyl, alkylthioalkyl, or aralkyl. (R represents one or more similar or different radicals, such as hydrogen, halogen, alkyl, :aikoxy, aikylthio, alkenyioxy, cyano, nitro, dialkylamino, or carbaikoxy, n is i to 5. and X represents oxygen or sulphur, processes for their manufacture and their use in pest control.

20 Claims, No Drawings THlOL AND DlTHlOl. CARBAMATF. ACID ESTER DERIVATIVES OF PHENYL FORMAMIDINE (Rai I wherein R, represents hydrogen. alkyl. alkenyl. alkinyl.

or aralkyl. R- represents alkyl. alkenyl. alkinyl. alkoxyalkyl. alkylthioalkyl. or aralkyl. (R,,),, represents one or more similar or different radicals. such as hydrogen. halogen. alkyl. alko xy. alkylthio. alkcnyloxy. cyuno. ni

tro. dialltylamino. or carbalkoxy. n is l to 5. and X represents oxygen or sulphur.

The alltyl. alkyloxy. alkoxyalkyl. alkylthio. alkylthioalkyl. alkenyl. alkenyloxy. alltinyl. or alltinyloxy groups that are possible for R,. R and R;, have I to 18. in particular I to l2. carbon atoms in the chain; the alkenyl and alltinyl chains have 3 to 18. but preferably 1 to 4 and 3 to 5 carbon atoms respectively. These groups can be straight-chain or branched. substituted or unsubstituted. Possible suhstituents are preferably halogen atoms. cyano. hydroxyl. alkoxy. and alkylthio groups. By halogen is meant fluorine. chlorine, bromine and/or iodine. Examples of such groups include: methyl. methoxy. methylthio. ethyl. ethylthio. ethoxy. trilluoromethyl. chloroethyl. chloroethyl. propyl. isopropyl. n-. i-. see. and tert. butyl. allyl. allyloxy. methallyl. propargyl. n-butinyl. isohutinyl.

Aralkyl groups represented by R, and R, are to be understood as meaning in particular benzyl or phenethyl groups that are unsubstituted or substituted by halogemespeeially by chlorine. alkyl with l to 4 carbon atoms and alkoxy with l to 4 carbon atoms. By carbalkosy as represented by R. is meant for example methoxycarbonyl.

Preferred compounds on account of their action are those ofthe formula I. wherein R, represents hydrogen. alkyl with l to 4 carbon atoms. alkenyl with 3 to 4 carbon atoms. alkinyl with 3 to 5 carbon atoms or unsubstituted benzyl. R represents alkyl with l to 4 carbon atoms. alkenyl with 3 to 4 carbon atoms. alkinyl with 3 to 5 carbon atoms. alkoxyalkyl with l to 4 carbon atoms in each of the moieties. unsubstituted benzyl or benzyl which is substituted by one or more chlorine atoms. (R;.),, represents one or more similar or different radicals. such as hydrogen. fluorine. chlorine. bromine. methyl. trilluoromethyl. methosy. methylthio. ethyl. ethos ethylthio. chlorocthyl. propyl. isopropyl. nbutyl. allyloxy. cyano. nitro. dimethylamino. or methoxycarbonyl. It is l to 3. and X represents oxygen or sulphur.

The compounds of the formula I can be manufactured c.g. by the following known methods: for thiocarbamate l'ormamltlincs:

1 N=('HN-H +Cl-- SR.,

lllll ain I R1 t ll l optionally acid acceptor Compounds of the formula I. wherein X U.

t l\' l a l" R,

acid acceptor Compounds of the formulal. wherein X 0. For dithiocarbamate formamidines:

acid acceptor Compounds of the formula I. wherein X S. ln the formulae II to IV. R,. R R,,. and n have the meanings given for the formula l.

Examples of suitable acid acceptors are: formami' dines of the formula ll; tertiary amines. such as triethyl' amine. dimethylaniline. pyridine. inorganic bases. such as hydroxides and carbonates of alkali and alkaline earth metals. preferably sodium and potassium carbon ate.

The reaction is carried out preferably in solvents or diluents which are inert towards the reactants. Examples of suitable solvents or diluents are: aromatic by droearbons. such as benzene. toluene. bcnzenes. halogenated hydrocarbons chlorobenzene. polychloroben zene. bromobenzene. chlorinated alkanes with l to 3 carbon atoms; others. such as dioxan, tetrahydrofuran; esters, such as ethyl acetate; ketones. such as methyl ethyl ketone. diethyl ketone. nitriles etc.

Some of the starting materials of the formula ll are known compounds which can be manufactured by methods which are known per se.

The compounds of the formula I display a broad bio cidal activity and can be used for combating diverse plant and animal pests and as abscission agents and defoliants.

In particular. however. they possess insecticidal and acaricidal properties and may be used against all development stages. c.g. eggs. larvae. pupae. nymphs and adults. of insects and representatives of the order Ace rina. for example agairist insects of the families: Blat tidac. Gryllidae. Gryllotalpidac. Tettigoniidae. Cimiel due. Phyrrhocoridac. Rcduviidac. Aphididac. Del phacidac. Diaspididae. Pscudoeoccidae. Chrysomeli dae. ('occincllidae. Brachidae. Scarabacidac. Dermes tidac. Tcnebrionidac. 'fineidac. Noctuidac. Lyman triidae. Pyralidae. Culicidac. Tripulidae. Stomoxydae Muscitlac. Calliphoridae. Trypctidae. Ptillcidae. as we as Acaridac of the families: lxodidae. Argasidae. Tetranychidae. Dermanyssidae.

The insecticidal or acaricidal action can be substan tially broadened and adapted to given circumstances by the addition ofother insecticides and/or acarieides. Examplcs of suitable additives are: organic phosphorus compounds. derivatives of nitrophenols. formamidincs. ureas. carbamates. and/or chlorinated hydrocarbons.

The active substances of the formula l are also suitable for combating representatives ofthc division Thallophyta. e.g. viruses. bacteria and fungi. They thus posscss fungicidal properties against phytophathogenic fungi on various cultivated plants. such as cereals. maize. rice. vegetables, ornamental plants. fruit trees. vines. farm products. etc.

With the new active substances it is possible to control or destroy fungi occurring on fruit. blossom. leaves. stems. tubers and roots. and from which parts of plants which grow later then also remain free. The active substances of the formula I are active in particular against phytopathogcnic fungi belonging to the following classes: Oomycetes. Zygomycetes. Ascomycetes. Basidiomycctes. Denteromycetes.

In addition. the new active substances can also be used for treating seeds. fruit. tubers etc.. and protecting them from fungus infections. for example from smut fungi ofall kinds. such as Ustilaginales. and for combating phytopathogenic nematodes.

The compounds ofthe formula I may be used as pure active substance or together with suitable carriers and- /or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in formulation technique, for example natural or regenerated substances. solvents. dispersants. wetting agents. adhesives. thickeners. binders and/or fertilisers.

For application. the compounds of the formula I may be processed to dusts. emulsion concentrates. granules. dispersions. sprays. to solutions. or suspensions. in the conventional formulation which is commonly cmploycd in application technology. Mention is also to be made of cattle dips and spray races. in which aqueous prepartions are used.

The agents according to the invention are manufacturcd in known manner by intimately mixing and/or grinding active substances of the formula l with the suitable carriers. o tionally with the addition of dispersants or solvents which are inert towards the active substances. The active substances may .take. and be used in. the following forms:

Solid forms:

Dusts. Tracking agents. granules. coated granules. impregnated granules and homogeneous granules.

Liquid forms:

a. activ substances which are dispersiblc in water: wcttable powders. pasts. emulsions:

b. solutions.

The content of active substance in the above de- (all The active substances are mixed with the carriers and ground.

Granules The following substances are used to produce 5% granules:

5 parts of active substance.

0.25 parts of epichlorohydrin.

0.25 parts of cetyl polyglycol ether.

3.50 parts of polyethylene glycol.

9] parts of kaolin (particle size 0.3 0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 partsofacctone; the polyethylene glycol and cetyl polyglycol ether are then added. The thus obtained solution is sprayed on kaolin. and the acetone subsequently evaporated in vacuo.

Wettable powoder:

The following constituents are used for the preparation of (a) a 407:. (b) and (c) a 25%. and (d) a I071 wcttable powder:

a. 40 parts of active substance.

5 parts of sodium lignin sulphonate.

1 part of sodium dibutyl-naphthalene sulphonate.

54 parts of silicic acid.

b. 25 parts of active substance.

4.5 parts of calcium lignin sulphonate.

1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (l:l

l.S parts of sodium dibutyl naphthalene sulphonate.

l9.5 parts of silicic acid.

l9.5 parts of Champagne chalk.

28.] parts of kaolin c. 25 parts of active substance.

2.5 parts of isooctylphenoxy-polyoxyethyleneethanol.

l.7 parts of Champagne chalk/hydroxyethyl ccllulose mixture (1:1). 8.3 parts of sodium aluminium silicate. l6.5 parts of kieselguhr. 46 parts of kaolin.

d. l0 parts of active substance.

3 parts ofa mixture oftlhe sodium salts of saturated fatty alcohol sulphates.

5 parts of naphthalcnesulphonic acid/formaldehyde condensate.

82 parts of kaolin.

The active substances are intimately mixed. in suitable mixers. with the additives. the mixture being then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.

Emulsifiable concentrates:

The following substances are used to produce (a) a NW: and (b) a 25V: cmulsifiable concentrate:

a. ll) parts of active substance.

3.4 parts of epoxidised vegetable oil.

l3.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylaryl sulphonatc calcium salt.

40 parts of dimethylformamide.

EXAMPLE 1 Manufacture of N-(2-methyl-4-chlorophenyl)- N'methyl-N'-benzyldithiocarbamoyl-formamidine 7.6 g of CS;- and ll g of triethylamine are added simultaneously with stirring to a solution of i8 g of N( 2- methyl-4-chlorophenyl)N'-methyl-formamidine in I50 ml of ethanol. the temperature being kept at 0C. Immediately afterwards l3 g ofbenzyi chloride are added. whereupon the temperature rises to 30C. The reaction mixture is stirred for l2 hours at room temperature. then poured into water and extracted with benzene. The benzene solution is dried over sodium sulphate and evaporated in vacuo. The resulting dark oil soon solidilies to a crystalline substance. Recrystallisation from methanol yields thecompound of the formula with a melting point of 96-99C.

The following compounds are also manufactured in analogous manner:

mp; 'm-au'c m.p.; "IS-79C m.p.: Xi-94C m.p.: 94:-95C

m.p.: 88-89C 3" EXAMPLE 2 Manufacture of N-(2.4-dimcthylphenyl)-N'-methyl- N'-sec. butyl-thiocarhamoyl-formumidine 23g of chlorothioformic acid sec. hutyl ester are added dropwise with stirring to a solution ol49 g ol- N- (2.4-dimethylphenyl)N'-methyl-formamidine in 350 m. of dry benzene. the temperature being kept at 5l()C. The reaction mixture is stirred for l2 hours. then the resulting hydrochloride salt of the l'orm'amidine simultaneously used as acid acceptor is filtered off. washed with benzene. and the benzene solution is evaporated in vacuo to give the compound of the formula 09 as a pale yellow Oll with a refractive index of n,,-"' l.5oh6. The following compounds are manufactured in analogous manner:

CH. ct N=CHN-C-SCH 1 n,, =t.ss2s

catan CH" l CH. N=CH--NCS-CH 1 n,,"-"=t.s3sn ll 2 3 a tul Cl N=ca-N-c -s-c,tt. m.p.: 74-75% Cl men ing-cat,

3 l C1 N=ca-ry-c-s-c.a.

3 t Cl N=cH--N-c--s-'c,tt.

N=CHN--(li-S cat. Cl

EXAMPLE 3 A. Insecticidal ingest poison action Cotton and potato plants were sprayed with a 0.05% aqueous emulsion (obtained from a 107: emulsifiable concentrate). After the coating had dried. the cotton plants were populated with Spodopu'ru lilmrult's or HelioI/risrviruscwts larvae L and the potato plants with C olorado potato beetle larvae (Lt'plinuturxzt dt'ccmlim'ulal. The test was carried out at 24C and 607: relative humidity. In the above test. the compounds according to Examples l and 2 displayed good ingest poison action against S/xn/oplcru Iilmrulis. Ileliot/tix and Lcptittulurxu (It't'llll/illl'U/(l.

B. Systemic insecticidal action To determine the systemic action. rooted bean plants lit-infitlnn') were put into a (LOW: aqueous active substance solution (obtained from a lW/i emulsiliable concentrate). After 24 hours. aphids (Apltis fitlnu') were placed on the parts of the plant above the soil. The

aphids were protected from contact and gas action by means of a special device. The test was carried out at 24C and 70'?! relative humidity. In the above tests the compounds accordingto Examples l and 2 displayed systemic insecticidal action against Apltis filhut'.

plied in granule form to the paddy \vater (rate of application: 8 kg of active substance per hectare). Evaluation of the insecticidal action took place lt) days after application of the granules.

The compounds according to Examples l and 2 were active in the above test against ('ln'lu .\'ll])[)!'('.\.\'tl.\'.

EXAMPLE 5 Action against soil insects Sterilised compost earth is homogeneously mixed with a wettable powder containing 25% of active substance so as to give concentrations of lb, 8. 4. 2. and l ppm. Young zuccetti and cabbage plants were planted in the prepared soil and immediately infested with 5 Aulumpltoru fi'morult's larvae (age: l5 d/2SC) and I5 C/torlup/tilu hruszvicuc (cabbage fly) eggs. A third corresponding soil sample is provided with slices of apple as feed and populated with S Pachnoda savignyi larvae (2t) d/25C).

Mortality inspection is carried out 10 days after application and infestation.

The screening test with caterpillars (Agrotis Y-L- proceeds in analogous manner. except that the concentrations are 40. 2t). and l() ppm. Mallow leaves are used as feed. In the above test. the compounds according to Examples l and 2 were active against Aulumphumfi'murn/is, ('Itormp/tilu hraxsicm'. Puc/mmlu .Sdt'iglt). and Agrotis larvae.

EXAMPLE 6 Action against ticks A. Rhipt'cephulus lmrsu Five adult ticks and 5t) tick larvae were counted into a glass tube and immersed for l to 2 minutes in 2 ml of an aqueous emulsion from an emulsion series each containing IOO lt). l and (H ppm of test substance. The tube was then sealed with a standardised cotton wool plug and placed on its head. so that the active substance emulsion could be adsorbed by the cotton wool. in the case of the adults evaluation took place after 2 weeks. and in that of the larvae after 2 days. Each test was repeated twice.

B. Bouphilus microplux (larvae) Tests were carried out in each case with 2() OP- sensitive larvae using an analogous dilution series as in the case of test A. (The resistence refers to the tolerability of Diazinon).

The compounds according to Examples 1 and 2 acted in these tests against adults and larvae ot- 'I'ItipiccplmIns bursa sensitive and OP-resistant larvae of Btmp/ti/lu mit'ruplus.

EXAMPLE 7 Acaraeitlal action Ilmscolux rulgurix (dwarf beans) have an infested piece of leaf from a mass culture of 'lelrunyclms' m'liuu' placed on them l2 hours before the test for the acaricidal action. The mobile stages which have migrated are sprayed with the emulsified test preparations from a chromatography atomiser so that the spray broth does not run off. The number of living and dead larvae. adults and eggs are evaluated after 2 to 7 days under a stereoscopic microscope and the result expressed in percentages. During the interim" the treated plants are kept in greenhouse compartments at 259C.

The compounds according to Examples l and 2 were active in the above test against eggs. larvae and adults of TL'!IUll \(/lll.t urlit'uc.

EXAMPLE 8 Action against soil nematodes To test the action against-soilnematodes. the active substance in the concentration indicated in each case is applied to and intimately mixed with soil infected with root gall nematodes (Meluidgyne Areuaria). lm-

mcdiately afterwards. tomato cuttings are planted in a the thus prepared soil in a series of tests and after a wherein R, represents hydrogen. alkyl with l to 4 carbon atoms. alkenyl with 3 to 4 carbon atoms. alkinyl with 3 to 5 carbon atoms or unsubstituted benzyl, R represents alky-l with J to 4carbon atoms. alkenyl with 3 to 4 carbon atoms. alkinyl with 3 to 5 carbon atoms. alkoxyalkyl with l to 4 carbon atoms in each of the moieties. alkylthioalkyl with l to 4 carbon atoms in each of the moieties. unsubstituted benzyl or benzyl which is substituted by one or more chlorine atoms, (R h, represents one or more similar or different radicals. selected from the group consisting of hydrogen. fluorine. chlorine. bromine. methyl. trifluoromethyl. methoxy. methylthio. ethyl. cthoxy. ethylthio. chlorocthyl. propyl. isopropyl. n-butyl. allyloxy. cyano. nitro. dimethylamino. or methoxycarbonyl. n is l to 3 and X represents oxygen or sulphur.

2. A compound according to claim l. of the formula 3. A compound according to claim I. of the formal 3 s Q I (l N=(H--NCSLH;-C ('H.

m 4 A compound according to claim I. of the formal 3 s I I5 (I N%'H-li '-CS-CH- ('=CH.

(H (I (I 5. A compound according to claim I. of the formu i rs=ch-ry-c-s-cn.-c '=cn,.

' cal. ct

6. A compound according to claim 1, of the formu 3 t s I I (I N H-T'( SC| SI( n l 7 a 7. A compound according to claim 1, of the forma a i v 40 (I N=(HN-(.'S--C"H -S-CH;..

CH;I

8. A compound according to claim I. of the form 45 i 3 s l CH. N=(H--bllC--S(H, I Ch. (l 1 c 9. A compound according to claim I. of the form CH 5s 3 i t- N= riz -cii, Q

10. A compound according to claim I. of the form H s 3 u (5 Cl .\'=('ti- (|'--S---(H- H. A compound according to claim I, of the formula I). A compound according to claim I. ofthc formula i N=CH---lilC-S--(H, c1. CH

S CH I N-(H--N('S-(H,CI('H,.

I CH, l2. A compound according to claim Lofthe formula CH i I7. A compound according to claim I, of the formula (I N=H-N--C-SCH,-C=(H=. I5

I 0 Ch, CH CH, 7

CH, -N='(HNC--S C1";

CH 13. A compound according to claim I, ofthe formula w i 5 18. A compound according to claim I, of the formula I Ha N=CH-N-C-SCH,-C I N.

l O CH I CH a (I N==('H-N-(.'-S CH3 I ('.,H,,

14. A compound according to claim I, of the formula 19. A compound according to claim I, of the formula (EH10) IS. A compound according to claim I, ofthe formula 20. A compound according to claim I, of the formula UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT N0. 3, 897,474

DATED July 29 1975 |NVENTOR(S) Georg Pissiotas It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 18 Claim 5, in the formula, change "N=Ch" to N=CH Column 18, Claim 8, in the formula, change "Ch to CH Column 19, Claim 12, in the formula, change "Ch to CH Column 19, Claim 14, in the formula, change "Ch to CH Column 19, Claim 15, in the formula, change "H to CH Signed and Scaled this fourth Day of May 1976 [SEAL] Arrest:

RUTH C. MASON I C. MARSHALL DANN Arresting Officer (ummissium'r uflaruns and Trademarks 

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